Three coordinate divalent Group 14 element compounds with a β-diketiminate as supporting ligand L2MX [L2=PhNC(Me)CHC(Me)NPh, X=Cl, I; M=Ge, Sn]

Akkari, A; Byrne, Janice J.; Saur, Isabelle; Rima, G.; Gornitzka, Heinz; Barrau, J.

doi:10.1016/s0022-328x(00)00893-7

Cited by 102 publications

(98 citation statements)

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“…91,96,101,102 Moreover, to our knowledge, no halogenated and also no nitrogen-substituted germanechalcogenones had been characterized until the recent work by our group. 92,93 It is noteworthy that during this work analogous germanochalcogenones have been reported by Roesky and co-workers. …”

supporting

confidence: 63%

“…Syntheses of the L 2 (X)GeY germanethione and selone 92,93 are very easy starting directly from the divalent species L 2 (X)Ge and elemental chalcogens (Eqn (3)).…”

Section: Synthesis Characterization and Structuresmentioning

confidence: 99%

“…Significant advances have now been encountered in this field, as illustrated by the various successful isolations and structural characterizations of such metallanechalcogenones. But, up until recently,92,93 only four germanethiones, 94 -98 seven germaneselones 95,98 -101 and four germanetellones 37,91,95,102 had been isolated at room temperature and characterized structurally. These compounds are either thermodynamically stabilized 37,94,95,97,99,100 by coordination of Lewis base to the germanium, or kinetically stabilized by bulky protecting groups on the germanium.…”

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Three‐coordinate divalent Group 14 element derivatives and related compounds

Saur

Alonso

Barrau

2005

Applied Organom Chemis

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INTRODUCTIONThis paper is an overview of a particular part of our systematic investigation of the divalent germanium and tin species focusing on the use in this chemistry of a β-diketiminato ligand with no encumbering aryl groups on the nitrogen. The bidentate three-atom bridging ligand L 2 (L 2 = PhNC(Me)CHC(Me)NPh), by its remarkable stabilizing properties, allows for easy isolation of subvalent germanium and tin compounds and, as such, permits a general insight on the chemistry of such species. The emphasis here will be on the divalent species L 2 (X)M (M = Ge, Sn), the germanechalcogenones L 2 (Cl)Ge Y, the transition- L (n−x) and the cationic ger- IntroductionThe divalent species of Group 14 elements are the heavier carbene analogues; for recent reviews, see Refs 6-10. They are generally transient species. As a general rule, when these species contain unfunctionalized organic ligands, they undergo rapid oligomerization and polymerization. In the last two decades, two principal methods of stabilization have been particularly investigated. Thus, various kinetically and/or thermodynamically stabilized divalent germanium and tin compounds have been isolated in a monomeric state. 1 -5,11 -81 The use of bulky groups bound to the Group 14 element to prevent aggregation permitted the first syntheses of stable monomer divalent species; the most noticeable are the dialkyl-germylene and -stannylene reported by Lappert and co-workers, 12 the first stable monomeric arylgermylene ((Mes * ) 2 Ge (Mes * = 2,4,6-t Bu 3 -phenyl)) described by Du Mont and co-workers, 14 and the well-known aryl-germylene and -stannylene Tbt(Tip)M 14 (M 14 = Ge, Sn; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Tip = 2,4,6-i Pr 3 -phenyl) of Okazaki and co-workers. 25,29The ligand backbone may also play an important role in improving stability. Thus, the presence of ligands with donor side arms on the germanium or the tin element can (by transfer of electron density) reduce the deficit on 37 is, to our knowledge, the first example of an intramolecular base stabilized homoleptic dialkylgermylene. Various amino-, phosphino-, thioalkoxy-, alkoxy-and aryloxy-divalent species have also been isolated in monomeric form owing to this method of stabilization; one should mention in particular the studies of Jutzi and co-workers, 28,32,54,71 Veith and coworkers, 15,18,40,66 Parkin and co-workers, 67 Jurkschat and co-workers, 77,78 Dias and co-workers 31,35,42,69,80,81 and Roesky and co-workers. Main Group Metal Compounds -5Although a large number of homoleptic divalent germanium and tin species have been isolated using these concepts of stabilization, there are fewer examples of heteroleptic compounds having been reported, though the first functional heteroleptic germylenes R(Cl)Ge (R = Et, Ph) were obtained as viscous oils in the 1970 by our group.6 Few solidstate structures of such heteroleptic compounds have been described. Noteworthy examples are in the area of thermodynamic stabilization, the acetylacetonatogermylene R(I)Ge (R = OC (Me) 46...

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supporting

confidence: 63%

“…Syntheses of the L 2 (X)GeY germanethione and selone 92,93 are very easy starting directly from the divalent species L 2 (X)Ge and elemental chalcogens (Eqn (3)).…”

Section: Synthesis Characterization and Structuresmentioning

confidence: 99%

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confidence: 99%

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Three‐coordinate divalent Group 14 element derivatives and related compounds

Saur

Alonso

Barrau

2005

Applied Organom Chemis

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“…Whereas Meller germylenes are divalent and dicoordinate heterocycles with two normal covalently bonded nitrogen atoms, there are NHGe that are tricoordinate and derived from the closely related monoimino germylene system. Examples of this include amidinates [17], aminotroponiminates [18] and ß-diketiminates [19,20] (see Scheme 2). They form ring systems with an even number of ring members (amidinates 4; ß-diketiminates 6; aminotroponiminates 10) and thus have to form a N-Ge normal covalent and a N-Ge coordinative bond in order to maintain a fully conjugated double bond system in the ring.…”

Section: Introductionmentioning

confidence: 99%

“…Their "empty" germanium p-orbitals can no longer be filled sufficiently by p-interaction with the adjacent nitrogen atoms (they have already partial donor bond character in the neutral molecules). The result is a pyramidal germanium centre exhibiting a weak coordination to the otherwise uncoordinating anion [19,20]. They act as Lewis acids.…”

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Can N-heterocyclic germylenes behave as Lewis acids - is there another side to Meller germylenes?

Kühl

2008

Open Chemistry

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N-Heterocyclic germylenes are known to exist in two structurally different forms, the planar Meller germylenes and the monoimino germylenes that feature an envelope structure. This essay reviews recent reports dealing with radical and cationic Meller type germylenes § featuring the monoimino germylene structure, discusses their transformations and relationships, and asks the question whether indeed N-heterocyclic germylenes can be turned into Lewis acids.© Versita Warsaw and Springer-Verlag Berlin Heidelberg.

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Germylenes

Nakata

2023

Organogermanium Compounds

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Three coordinate divalent Group 14 element compounds with a β-diketiminate as supporting ligand L2MX [L2=PhNC(Me)CHC(Me)NPh, X=Cl, I; M=Ge, Sn]

Cited by 102 publications

References 35 publications

Three‐coordinate divalent Group 14 element derivatives and related compounds

Three‐coordinate divalent Group 14 element derivatives and related compounds

Can N-heterocyclic germylenes behave as Lewis acids - is there another side to Meller germylenes?

Germylenes

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